High vinyl terminated propylene based oligomers

ABSTRACT

This invention relates to a co-oligomer having an Mn of 300 to 30,000 g/mol comprising 10 to 90 mol % propylene and 10 to 90 mol % of ethylene, wherein the oligomer has at least X % allyl chain ends, where: 1) X=(−0.94 (mole % ethylene incorporated)+100), when 10 to 60 mole % ethylene is present in the co-oligomer, and 2) X=45, when greater than 60 and less than 70 mole % ethylene is present in the co-oligomer, and 3) X=(1.83*(mole % ethylene incorporated)−83), when 70 to 90 mole % ethylene is present in the co-oligomer. This invention also relates to a homo-oligomer, comprising propylene, wherein the oligomer has: at least 93% allyl chain ends, an Mn of about 500 to about 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 100 ppm aluminum. This invention also relates to a process of making homo-oligomer, comprising propylene, wherein the productivity is greater than 4500 g/mmol Hf (or Zr)/hour.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Pat. No. 8,372,930, issued Feb.12, 2013.

FIELD OF THE INVENTION

This invention relates to olefin oligomerization, particularlypropylene-ethylene oligomerization, to produce vinyl terminatedoligomers.

BACKGROUND OF THE INVENTION

Alpha-olefins, especially those containing about 6 to about 20 carbonatoms, have been used as intermediates in the manufacture of detergentsor other types of commercial products. Such alpha-olefins have also beenused as monomers, especially in linear low density polyethylene.Commercially produced alpha-olefins are typically made by oligomerizingethylene. Longer chain alpha-olefins, such as vinyl-terminatedpolyethylenes are also known and can be useful as building blocksfollowing functionalization or as macromonomers.

Allyl terminated low molecular weight solids and liquids of ethylene orpropylene have also been produced, typically for use as branches inpolymerization reactions. See, for example, Rulhoff, Sascha andKaminsky, (“Synthesis and Characterization of Defined BranchedPoly(propylene)s with Different Microstructures by Copolymerization ofPropylene and Linear Ethylene Oligomers (C _(n)=26-28) withMetallocenes/MAO Catalysts,” Macromolecules 16 2006, 1450-1460), andKaneyoshi, Hiromu et al. (“Synthesis of Block and Graft Copolymers withLinear Polyethylene Segments by Combination of Degenerative TransferCoordination Polymerization and Atom Transfer Radical Polymerization,”Macromolecules 38 2005, 5425-5435).

Further, U.S. Pat. No. 4,814,540 discloses bis(pentamethylcyclopentadienyl)hafnium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride and bis(tetramethyl n-butylcyclopentadienyl)hafnium dichloride with methylalumoxane in toluene orhexane with or without hydrogen to make allylic vinyl terminatedpropylene homo-oligomers having a low degree of polymerization of 2-10.These oligomers do not have high Mn's and have at least 93% allylicvinyl unsaturation. Likewise, these oligomers lack comonomer and areproduced at low productivities with a large excess of alumoxane (molarratio ≧600 Al/M; M=Zr, Hf). Additionally, no less than 60 wt % solvent(solvent+propylene basis) is present in all of the examples.

Teuben et al. (J. Mol. Catal. 62 1990, 277-87) used[Cp*₂MMe(THT)]+[BPh₄], M=Zr and Hf) to make propylene oligomers. ForM=Zr a broad product distribution with oligomers up to C₂₄ (Mn 336) wasobtained at room temperature. Whereas for M=Hf only the dimer4-methyl-1-pentene and the trimer 4,6-dimethyl-1-heptene were formed.The dominant termination mechanism appeared to be beta-methyl transferfrom the growing chain back to the metal center, as was demonstrated bydeuterium labeling studies.

X. Yang, et al. (Angew. Chem. Intl Edn. Engl. 31 1992 1375) disclosesamorphous, low molecular weight polypropylene made at low temperatureswhere the reactions showed low activity and product having 90% allylicvinyls, relative to all unsaturations, by ¹H NMR. Thereafter, Resconi,et al. (J. Am. Chem. Soc. 114 1992, 1025-1032), disclose the use ofbis(pentamethylcyclopentadienyl)zirconium andbis(pentamethylcyclopentadienyl)hafnium centers to polymerize propyleneand obtained beta-methyl termination resulting in oligomers and lowmolecular weight polymers with “mainly allyl- and iso-butyl-terminated”chains. As is the case in U.S. Pat. No. 4,814,540, the oligomersproduced do not have at least 93% allyl chain ends, an Mn of about 500to about 20,000 g/mol (as measured by ¹H NMR), and the catalyst has lowproductivity (1-12,620 g/mmol metallocene.hr;>3000 wppm Al in products).

Similarly, Small and Brookhart, (Macromol. 32 1999, 2322) discloses theuse of a pyridylbis amido iron catalyst in a low temperaturepolymerization to produce low molecular weight amorphous propylenematerials apparently having predominant or exclusive 2,1 chain growth,chain termination via beta-hydride elimination, and high amounts ofvinyl end groups. Dekmezian et al. (Macromol. 33, 2000, 8541-8548)discloses materials with up to about 81 percent vinyl termination madeusing dimethylsilyl bis(2-methyl, 4-phenyl-indenyl)hafnium dichlorideand methylalumoxane in toluene at about 120° C. The materials have anumber average molecular weight of about 12,300 (measured with ¹H NMR)and a melting point of about 143° C.

Moscardi et al. (Organomet. 20, 2001, 1918) discloses the use ofrac-dimethylsilylmethylene bis(3-t-butyl indenyl)zirconium dichloridewith methylalumoxane in batch polymerizations of propylene to producematerials where “ . . . allyl end group always prevails over any otherend groups, at any [propene].” In these reactions, morphology controlwas limited and approximately 60% of the chain ends are allylic.

Coates et al. (Macromol 2005 38, 6259) discloses preparation of lowmolecular weight syndiotactic polypropylene ([rrrr]=0.46-0.93) withabout 100% allyl end groups using bis(phenoxyimine)titanium dichloride((PHI)₂TiCl₂) activated with modified methyl alumoxane (MMAO; Al/Timolar ratio=200) in batch polymerizations run between −20 and +20° C.for four hours. For these polymerizations, propylene was dissolved intoluene to create a 1.65 M toluene solution. Catalyst productivity wasvery low (0.95 to 1.14 g/mmol Ti/hr).

JP-2005-336092-A2 discloses the manufacture of vinyl-terminatedpropylene polymers using materials such as H₂SO₄ treatedmontmorillonite, triethylaluminum, triisopropyl aluminum, where theliquid propylene is fed into a catalyst slurry in toluene. This processproduces substantially isotactic macromonomers not having a significantamount of amorphous material.

Rose et al (Macromolecules 2008, 41, 559-567) disclosespoly(ethylene-co-propylene) macromonomers not having significant amountsof iso-butyl chain ends. Those were made with bis(phenoxyimine) titaniumdichloride ((PHI)₂TiCl₂) activated with modified methylalumoxane (MMAO;Al/Ti molar ratio range 150 to 292) in semi-batch polymerizations (30psi propylene added to toluene at 0° C. for 30 min, followed by ethylenegas flow at 32 psi of over-pressure at about 0° C. for polymerizationtimes of 2.3 to 4 hours to produce E-P copolymer having an Mn of about4800 to 23,300. In four reported copolymerizations, allylic chain endsdecreased with increasing ethylene incorporation roughly according tothe equation:% allylic chain ends(of total unsaturations)=−0.95(mole % ethyleneincorporated)+100.For example, 65% allyl (compared to total unsaturation) was reported forE-P copolymer containing 29 mole % ethylene. This is the highest allylpopulation achieved. For 64 mole % incorporated ethylene, only 42% ofthe unsaturations are allylic. Productivity of these polymerizationsranged from 0.78×10² g/mmol Ti/hr to 4.62×10² g/mmol Ti/hr.

Prior to this work, Zhu et al. reported only low (˜38%) vinyl terminatedethylene-propylene copolymer made with the constrained geometrymetallocene catalyst [C₅Me₄(SiMe₂N-tert-butyl)TiMe₂ activated withB(C₆F₅)₃ and MMAO (Macromol 2002 35, 10062-10070 and Macromol Rap.Commun. 2003 24 311-315).

Janiak and Blank summarize a variety of work related to oligomerizationof olefins (Macromol. Symp. 236 2006, 14-22).

In all the prior art no catalysts are shown to produce high allylicchain unsaturations in high yields, a wide range of molecular weight,and with high productivity for propylene-based polymerizations,especially propylene-ethylene copolymerizations. Thus, there is still aneed for propylene based macromonomers that have allyl terminationpresent in high amounts (90% or more), with control over a wide range ofmolecular weights that can be made at commercial temperatures (e.g. 25°C. and above) and commercial rates (5,000 g/mmol/hr productivity ormore). Alternately, there is a need for propylene ethylene oligomershaving structural robustness (where addition of ethylene raisesviscosity and the solubility parameter—relative to propylene—andprovides for potential crystallizable ethylene runs, while loweringglass transition temperature). Further, there is a need for propylenebased reactive materials having vinyl termination which can befunctionalized and used in additive applications.

SUMMARY OF THE INVENTION

This invention relates to a propylene co-oligomer having an Mn of 300 to30,000 g/mol (as measured by ¹H NMR) comprising 10 to 90 mol % propyleneand 10 to 90 mol % of ethylene, wherein the oligomer has at least X %allyl chain ends (relative to total unsaturations), where: 1)X=(−0.94*(mole % ethylene incorporated)+100), when 10 to 60 mole %ethylene is present in the co-oligomer, and 2) X=45, when greater than60 and less than 70 mole % ethylene is present in the co-oligomer, and3) X=(1.83*(mole % ethylene incorporated)−83), when 70 to 90 mole %ethylene is present in the co-oligomer.

This invention further relates to a propylene oligomer, comprising morethan 90 mol % propylene and less than 10 mol % ethylene, wherein theoligomer has: at least 93% allyl chain ends, an Mn of about 500 to about20,000 g/mol (as measured by ¹H NMR), an isobutyl chain end to allylicvinyl group ratio of 0.8:1 to 1.35:1.0, and less than 1400 ppm aluminum.

This invention further relates to a propylene oligomer, comprising atleast 50 mol % propylene and from 10 to 50 mol % ethylene, wherein theoligomer has: at least 90% allyl chain ends, Mn of about 150 to about10,000 g/mol (as measured by ¹H NMR), and an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.3:1.0, wherein monomers havingfour or more carbon atoms are present at from 0 to 3 mol %.

This invention further relates to a propylene oligomer, comprising atleast 50 mol % propylene, from 0.1 to 45 mol % ethylene, and from 0.1 to5 mol % C4 to C12 olefin, wherein the oligomer has: at least 87% allylchain ends (alternately at least 90%), an Mn of about 150 to about10,000 g/mol, (as measured by ¹H NMR), and an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.35:1.0.

This invention further relates to a propylene oligomer, comprising atleast 50 mol % propylene, from 0.1 to 45 mol % ethylene, and from 0.1 to5 mol % diene, wherein the oligomer has: at least 90% allyl chain ends,an Mn of about 150 to about 10,000 g/mol (as measured by ¹H NMR), and anisobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.

This invention further relates to a homooligomer, comprising propylene,wherein the oligomer has: at least 93% allyl chain ends, an Mn of about500 to about 20,000 g/mol (as measured by ¹H NMR), an isobutyl chain endto allylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppmaluminum.

This invention further relates to a homogeneous process to make sucholigomers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of percent allylic chain ends versus mole % ethylenefor Examples 35 and 52 to 61. (The triangles are data fromMacromolecules 2008, 41, 559-567. The squares represent Examples 52 to61 and the circle represents Example 35.)

FIG. 2 is a chart of the range of chemical shift assignments for theisobutyl chain ends for the E-P copolymers.

DETAILED DESCRIPTION

This invention relates to a propylene homo oligomer, comprisingpropylene and less than 0.5 wt % comonomer, preferably 0 wt % comonomer,wherein the oligomer has:

-   -   i) at least 93% allyl chain ends (preferably at least 95%,        preferably at least 97%, preferably at least 98%);    -   ii) a number average molecular weight (Mn) of about 500 to about        20,000 g/mol, as measured by ¹H NMR (preferably 500 to 15,000,        preferably 700 to 10,000, preferably 800 to 8,000 g/mol,        preferably 900 to 7,000, preferably 1000 to 6,000, preferably        1000 to 5,000);    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.3:1.0;    -   iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,        preferably less than 1000 ppm, preferably less than 500 ppm,        preferably less than 100 ppm).

This invention relates to a propylene co-oligomer having an Mn of 300 to30,000 g/mol as measured by ¹H NMR (preferably 400 to 20,000, preferably500 to 15,000, preferably 600 to 12,000, preferably 800 to 10,000,preferably 900 to 8,000, preferably 900 to 7,000 g/mol), comprising 10to 90 mol % propylene (preferably 15 to 85 mol %, preferably 20 to 80mol %, preferably 30 to 75 mol %, preferably 50 to 90 mol %) and 10 to90 mol % (preferably 85 to 15 mol %, preferably 20 to 80 mol %,preferably 25 to 70 mol %, preferably 10 to 50 mol %) of one or morealpha-olefin comonomers (preferably ethylene, butene, hexene, or octene,preferably ethylene), wherein the oligomer has at least X % allyl chainends (relative to total unsaturations), where: 1) X=(−0.94*(mole %ethylene incorporated)+100{alternately 1.20 (−0.94 (mole % ethyleneincorporated)+100), alternately 1.50(−0.94 (mole % ethyleneincorporated)+100)}), when 10 to 60 mole % ethylene is present in theco-oligomer, and 2) X=45 (alternately 50, alternately 60), when greaterthan 60 and less than 70 mole % ethylene is present in the co-oligomer,and 3) X=(1.83*(mole % ethylene incorporated)−83, {alternately 1.20[1.83*(mole % ethylene incorporated)−83], alternately 1.50 [1.83*(mole %ethylene incorporated)−83]}), when 70 to 90 mole % ethylene is presentin the co-oligomer.

Alternately X is 80% or more, preferably 85% or more, preferably 90% ormore, preferably 95% or more.

In an alternate embodiment the oligomer has at least 80% isobutyl chainends (based upon the sum of isobutyl and n-propyl saturated chain ends),preferably at least 85% isobutyl chain ends, preferably at least 90%isobutyl chain ends. Alternately, the oligomer has an isobutyl chain endto allylic vinyl group ratio of 0.8:1 to 1.35:1.0, preferably 0.9:1 to1.20:1.0, preferably 0.9:1.0 to 1.1:1.0.

This invention relates to a propylene oligomer, comprising more than 90mol % propylene (preferably 95 to 99 mol %, preferably 98 to 9 mol %)and less than 10 mol % ethylene (preferably 1 to 4 mol %, preferably 1to 2 mol %), wherein the oligomer has:

at least 93% allyl chain ends (preferably at least 95%, preferably atleast 97%, preferably at least 98%);

a number average molecular weight (Mn) of about 400 to about 30,000g/mol, as measured by ¹H NMR (preferably 500 to 20,000, preferably 600to 15,000, preferably 700 to 10,000 g/mol, preferably 800 to 9,000,preferably 900 to 8,000, preferably 1000 to 6,000);

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0,and

less than 1400 ppm aluminum, (preferably less than 1200 ppm, preferablyless than 1000 ppm, preferably less than 500 ppm, preferably less than100 ppm).

This invention also relates to a propylene oligomer, comprising:

at least 50 (preferably 60 to 90, preferably 70 to 90) mol % propyleneand from 10 to 50 (preferably 10 to 40, preferably 10 to 30) mol %ethylene, wherein the oligomer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

an Mn of about 150 to about 20,000 g/mol, as measured by ¹H NMR(preferably 200 to 15,000, preferably 250 to 15,000, preferably 300 to10,000, preferably 400 to 9,500, preferably 500 to 9,000, preferably 750to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.3:1.0,wherein monomers having four or more carbon atoms are present at from 0to 3 mol % (preferably at less than 1 mol %, preferably less than 0.5mol %, preferably at 0 mol %).

This invention further relates to a propylene oligomer, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % C₄ to C₁₂ olefin (such as butene,hexene or octene, preferably butene), wherein the oligomer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 15,000g/mol, as measured by ¹H NMR (preferably 200 to 12,000, preferably 250to 10,000, preferably 300 to 10,000, preferably 400 to 9500, preferably500 to 9,000, preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0.

This invention further relates to a propylene oligomer, comprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % diene (such as C4 to C12 alpha-omegadienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene),wherein the oligomer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 20,000g/mol, as measured by ¹H NMR (preferably 200 to 15,000, preferably 250to 12,000, preferably 300 to 10,000, preferably 400 to 9,500, preferably500 to 9,000, preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.

Any of the oligomers prepared herein preferably have less than 1400 ppmaluminum, preferably less than 1000 ppm aluminum, preferably less than500 ppm aluminum, preferably less than 100 ppm aluminum, preferably lessthan 50 ppm aluminum, preferably less than 20 ppm aluminum, preferablyless than 5 ppm aluminum.

This invention also relates to a homogeneous process, preferably a bulkprocess, to make such oligomers.

As used herein, the term “oligomer” is defined to have an Mn of from 100to 25,000 g/mol as measured by ¹H NMR. When an oligomer is referred toas comprising an olefin, the olefin present in the oligomer is theoligomerized form of the olefin. A propylene oligomer is an oligomerhaving at least 50 mole % of propylene. A co-oligomer is an oligomercomprising at least two different monomer units (such as propylene andethylene). A homo-oligomer is an oligomer comprising units of the samemonomer (such as propylene). As used herein, Mn is number averagemolecular weight (measured by ¹H NMR unless stated otherwise, as forexample in Table 3A), Mw is weight average molecular weight (measured byGel Permeation Chromatography), and Mz is z average molecular weight(measured by Gel Permeation Chromatography), wt % is weight percent, andmol % is mole percent. Molecular weight distribution (MWD) is defined tobe Mw (measured by Gel Permeation Chromatography) divided by Mn(measured by ¹H NMR). Unless otherwise noted, all molecular weight units(e.g., Mw, Mn, Mz) are g/mol.

“Allyl chain ends” is defined to be an oligomer having at least oneterminus represented by (CH₂CH—CH₂-oligomer), formula I:

where the “•••” represents the oligomer chain. In a preferred embodimentthe allyl chain ends is represented by the formula II:

The amount of allyl chain ends is determined using ¹H NMR at 120° C.using deuterated tetrachloroethane as the solvent on a 500 MHz machine.and in selected cases confirmed by ¹³C NMR. Resconi has reported protonand carbon assignments (neat perdeuterated tetrachloroethane used forproton spectra while a 50:50 mixture of normal and perdeuteratedtetrachloroethane was used for carbon spectra; all spectra were recordedat 100° C. on a Bruker AM 300 spectrometer operating at 300 MHz forproton and 75.43 MHz for carbon) for vinyl terminated propyleneoligomers in J American Chemical Soc 114 1992, 1025-1032 that are usefulherein.

“Isobutyl chain end” is defined to be an oligomer having at least oneterminus represented by the formula:

where M represents the oligomer chain. In a preferred embodiment, theisobutyl chain end is represented by one of the following formulae:

where M represents the oligomer chain.

The percentage of isobutyl end groups is determined using ¹³C NMR (asdescribed in the example section) and the chemical shift assignments inResconi et al, J Am. Chem. Soc. 1992, 114, 1025-1032 for 100% propyleneoligomers and set forth in FIG. 2 for E-P oligomers.

The “isobutyl chain end to allylic vinyl group ratio” is defined to bethe ratio of the percentage of isobutyl chain ends to the percentage ofallylic vinyl groups.

In a preferred embodiment, the propylene oligomer comprises less than 3wt % of functional groups selected from hydroxide, aryls and substitutedaryls, halogens, alkoxys, carboxylates, esters, acrylates, oxygen,nitrogen, and carboxyl, preferably less than 2 wt %, more preferablyless than 1 wt %, more preferably less than 0.5 wt %, more preferablyless than 0.1 wt %, more preferably 0 wt %, based upon the weight of theoligomer.

The oligomer preferably has an M_(n) as determined by ¹H NMR of 150 to25,000 g/mole, 200 to 20,000 g/mol, preferably 250 to 15,000 g/mol,preferably 300 to 15,000 g/mol, preferably 400 to 12,000 g/mol,preferably 750 to 10,000 g/mol. Further a desirable molecular weightrange can be any combination of any upper molecular weight limit withany lower molecular weight limit described above. M_(n) is determinedaccording to the methods described below in the examples section.

The oligomer preferably has a glass transition temperature (Tg) of 0° C.or less (as determined by differential scanning calorimetry as describedbelow), preferably −10° C. or less, more preferably −20° C. or less,more preferably −30° C. or less, more preferably −50° C. or less.

The oligomer preferably contains less than 80 weight % of C₄ olefin(s),(such as isobutylene n-butene, 2-butene, isobutylene, and butadiene),based upon the weight of the oligomer, preferably less than 10 wt %,preferably 5 wt %, preferably less than 4 wt %, preferably less than 3wt %, preferably less than 2 wt %, preferably less than 1 wt %,preferably less than 0.5 wt %, preferably less than 0.25 wt % of C₄olefin(s) based upon the weight of the oligomer.

Alternately, the oligomer preferably contains less than 20 weight % ofC₄ or more olefin(s), (such as C₄ to C₃₀ olefins, typically such as C₄to C₁₂ olefins, typically such as C₄, C₆, C₈, C₁₂, olefins, etc.), basedupon the weight of the oligomer, preferably less than 10 wt %,preferably 5 wt %, preferably less than 4 wt %, preferably less than 3wt %, preferably less than 2 wt %, preferably less than 1 wt %,preferably less than 0.5 wt %, preferably less than 0.25 wt % of C₄olefin(s) based upon the weight of the oligomer, as determined by ¹³CNMR.

In another embodiment, the oligomer composition produced comprises atleast 50 wt % (preferably at least 75 wt %, preferably at least 90 wt %,based upon the weight of the oligomer composition) olefins having atleast 36 carbon atoms (preferably at least 51 carbon atoms, preferablyat least 102 carbon atoms) as measured by ¹H NMR assuming oneunsaturation per chain.

In another embodiment, the oligomer composition produced comprises lessthan 20 wt % dimer and trimer (preferably less than 10 wt %, preferablyless than 5 wt %, more preferably less than 2 wt %, based upon theweight of the oligomer composition), as measured by GC.

In another embodiment, the oligomer produced here contains less than 25ppm hafnium, preferably less than 10 ppm hafnium, preferably less than 5ppm hafnium based on the yield of polymer produced and the mass ofcatalyst employed.

In another embodiment, the oligomers described herein may have a meltingpoint (DSC first melt) of from 60 to 130° C., alternately 50 to 100° C.In another embodiment, the oligomers described herein have no detectablemelting point by DSC following storage at ambient temperature (23° C.)for at least 48 hours.

Melting temperature (T_(m)) and glass transition temperature (Tg) aremeasured using Differential Scanning calorimetry (DSC) usingcommercially available equipment such as a TA Instruments 2920 DSC.Typically, 6 to 10 mg of the sample, that has been stored at roomtemperature for at least 48 hours, is sealed in an aluminum pan andloaded into the instrument at room temperature. The sample isequilibrated at 25° C., then it is cooled at a cooling rate of 10°C./min to −80° C. The sample is held at −80° C. for 5 min and thenheated at a heating rate of 10° C./min to 25° C. The glass transitiontemperature is measured from the heating cycle. Alternatively, thesample is equilibrated at 25° C., then heated at a heating rate of 10°C./min to 150° C. The endothermic melting transition, if present, isanalyzed for onset of transition and peak temperature. The meltingtemperatures reported are the peak melting temperatures from the firstheat unless otherwise specified. For samples displaying multiple peaks,the melting point (or melting temperature) is defined to be the peakmelting temperature (i.e., associated with the largest endothermiccalorimetric response in that range of temperatures) from the DSCmelting trace.

In another embodiment, the oligomers described herein are a liquid at25° C.

In another embodiment, the oligomers described herein have an Mw(measured as described below) of 1,000 to about 30,000 g/mol,alternately 2000 to 25,000 g/mol, alternately 3,000 to 20,000 g/moland/or an Mz of about 1700 to about 150,000 g/mol, alternately 800 to100,000 g/mol.

Mw and Mz are measured by using a High Temperature Size ExclusionChromatograph (either from Waters Corporation or Polymer Laboratories),equipped with a differential refractive index detector (DRI),Experimental details, are described in: T. Sun, P. Brant, R. R. Chance,and W. W. Graessley, Macromolecules, Volume 34, Number 19, 6812-6820,(2001) and references therein. Three Polymer Laboratories PLgel 10 mmMixed-B columns are used. The nominal flow rate is 0.5 cm³/min, and thenominal injection volume is 300 μL. The various transfer lines, columnsand differential refractometer (the DRI detector) are contained in anoven maintained at 135° C. Solvent for the SEC experiment is prepared bydissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4liters of Aldrich reagent grade 1, 2, 4 trichlorobenzene (TCB). The TCBmixture is then filtered through a 0.7 μm glass pre-filter andsubsequently through a 0.1 μm Teflon filter. The TCB is then degassedwith an online degasser before entering the SEC. Polymer solutions areprepared by placing dry polymer in a glass container, adding the desiredamount of TCB, then heating the mixture at 160° C. with continuousagitation for about 2 hours. All quantities are measuredgravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/ml at room temperatureand 1.324 g/ml at 135° C. The injection concentration is from 1.0 to 2.0mg/ml, with lower concentrations being used for higher molecular weightsamples. Prior to running each sample the DRI detector and the injectorare purged. Flow rate in the apparatus is then increased to 0.5ml/minute, and the DRI is allowed to stabilize for 8 to 9 hours beforeinjecting the first sample. The concentration, c, at each point in thechromatogram is calculated from the baseline-subtracted DRI signal,I_(DRI), using the following equation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymersand 0.1 otherwise. Units on parameters throughout this description ofthe SEC method are such that concentration is expressed in g/cm³,molecular weight is expressed in g/mole, and intrinsic viscosity isexpressed in dL/g.

Molecular weight distribution (Mw/Mn—by GPC-DRI) is determined by themethod above. In some embodiments, the oligomers of this invention havean Mw/Mn (by GPC-DRI) of 1.5 to 20, alternately 1.7 to 10.

Oligomerization Process

This invention also relates to a homogeneous process, preferably a bulkprocess, to make the oligomers described herein. In a preferredembodiment, propylene and optional comonomers (such as ethylene) can beoligomerized by reacting a catalyst system (comprising metallocenecompound(s), and one or more activators) with the olefins. Otheradditives may also be used, as desired, such as scavengers and/orhydrogen. Any conventional suspension, homogeneous bulk, solution,slurry, or high-pressure oligomerization process can be used. Suchprocesses can be run in a batch, semi-batch, or continuous mode. Suchprocesses and modes are well known in the art. Homogeneouspolymerization processes are preferred. (A homogeneous polymerizationprocess is defined to be a process where at least 90 wt % of the productis soluble in the reaction media.) A bulk homogeneous process isparticularly preferred. (A bulk process is defined to be a process wheremonomer concentration in all feeds to the reactor is 70 volume % ormore.) Alternately no solvent or diluent is present or added in thereaction medium, (except for the small amounts used as the carrier forthe catalyst system or other additives, or amounts typically found withthe monomer; e.g. propane in propylene).

Suitable diluents/solvents for oligomerization include non-coordinating,inert liquids. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof such as can be foundcommercially (Isopars); perhalogenated hydrocarbons such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, and 1-decene. Mixtures of the foregoing are also suitable.

In a preferred embodiment, the feed concentration for theoligomerization is 60 volume % solvent or less, preferably 40 volume %or less, preferably 20 volume % or less. Preferably the oligomerizationis run in a bulk process.

Suitable additives to the oligomerization process can include one ormore scavengers, promoters, modifiers, reducing agents, oxidizingagents, hydrogen, aluminum alkyls, or silanes.

In a preferred embodiment hydrogen is present in the oligomerizationreactor at a partial pressure of 0.001 to 50 psig, preferably from 0.01to 25 psig, more preferably 0.1 to 10 psig. It has been found that inthe present systems, hydrogen can be used to provide increased activitywithout significantly impairing the catalyst's ability to produceallylic chain ends. Preferably the catalyst activity (calculated asg/mmolcatalyst/hr) is at least 20% higher than the same reaction withouthydrogen present, preferably at least 50% higher, preferably at least100% higher.

In an alternate embodiment, the productivity at least 4500 g/mmol/hour,preferably 5000 or more g/mmol/hour, preferably 10,000 or moreg/mmol/hr, preferably 50,000 or more g/mmol/hr.

In an alternate embodiment, the productivity is at least 80,000g/mmol/hr, preferably at least 150,000 g/mmol/hr, preferably at least200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably atleast 300,000 g/mmol/hr.

Preferred oligomerizations can be run at typical temperatures and/orpressures, such as from 25 to 150° C., preferably 40 to 120° C.,preferably 45 to 80° C., and preferably from 0.35 to 10 MPa, preferablyfrom 0.45 to 6 MPa, preferably from 0.5 to 4 MPa.

In a typical oligomerization, the residence time of the reaction is upto 60 minutes, preferably between 5 to 50 minutes, preferably 10 to 40minutes.

Catalyst Compound

Catalyst compounds useful herein include one or more metallocenecompound(s) represented by the formulae:

where

-   Hf is hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each Q is, independently carbon or a heteroatom, preferably C, N, P,    S (preferably at least one Q is a heteroatom, alternately at least    two Q's are the same or different heteroatoms, alternately at least    three Q's are the same or different heteroatoms, alternately at    least four Q's are the same or different heteroatoms);-   each R¹ is, independently, hydrogen or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹ may the same or    different as R²;-   each R² is, independently, hydrogen or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided that at    least one of R¹ or R² is not hydrogen, preferably both of R¹ and R²    are not hydrogen, preferably R¹ and/or R² are not branched;-   each R³ is, independently, hydrogen, or a substituted or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    preferably 1 to 6 carbon atoms, preferably a substituted or    unsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however that    at least three R³ groups are not hydrogen (alternately four R³    groups are not hydrogen, alternately five R³ groups are not    hydrogen);-   {Alternately, when the catalyst compound is to used to make the    homo-oligomer then each R³ is, independently, hydrogen, or a    substituted or unsubstituted hydrocarbyl group having from 1 to 8    carbon atoms, preferably 1 to 6 carbon atoms, preferably a    substituted or unsubstituted C₁ to C₈ linear alkyl group, preferably    methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, provided    however that: 1) all five R³ groups are methyl, or 2) four R³ groups    are not hydrogen and at least one R³ group is a C₂ to C₈ substituted    or unsubstituted hydrocarbyl (preferably at least two, three, four    or five R³ groups are a C₂ to C₈ substituted or unsubstituted    hydrocarbyl)};-   each R⁴ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group, preferably a substituted or unsubstituted    hydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to    8 carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, substituted phenyl (such as propyl phenyl),    phenyl, silyl, substituted silyl, (such as CH₂SiR′, where R′ is a C₁    to C₁₂ hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl);-   R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided however that    at least seven R⁷ groups are not hydrogen, alternately at least    eight R⁷ groups are not hydrogen, alternately all R⁷ groups are not    hydrogen, (preferably the R⁷ groups at the 3 and 4 positions on each    Cp ring of Formula IV are not hydrogen);-   N is nitrogen;-   T is a bridge, preferably, Si or Ge, preferably Si;-   each R^(a), is independently, hydrogen, halogen or a C1 to C20    hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) can    form a cyclic structure including aromatic, partially saturated, or    saturated cyclic or fused ring system;-   and further provided that any two adjacent R groups may form a fused    ring or multicenter fused ring system where the rings may be    aromatic, partially saturated or saturated.

The term “substituted” means that a hydrogen group has been replacedwith a hydrocarbyl group, a heteroatom or a heteroatom containing group.For example methyl cyclopentadiene (Cp) is a Cp group substituted with amethyl group and ethyl alcohol is an ethyl group substituted with an —OHgroup.

In an alternate embodiment, at least one R⁴ group is not hydrogen,alternately at least two R⁴ groups are not hydrogen, alternately atleast three R⁴ groups are not hydrogen, alternately at least four R⁴groups are not hydrogen, alternately all R⁴ groups are not hydrogen.

Catalyst compounds that are particularly useful in this inventioninclude one or more of:

-   (1,3-Dimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3,4,7-Tetramethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Dimethylindenyl)(tetramethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Diethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Dipropylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1-Methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Dimethylindenyl)(tetramethylpropylcyclopentadienyl)Hafniumdimethyl,-   (1,2,3-Trimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (1,3-Dimethylbenzindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (2,7-Bis    t-butylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (9-Methylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   (2,7,9-Trimethylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,-   μ-Dihydrosilyl(bis tetramethylcyclopentadienyl)Hafniumdimethyl,-   μ-Dihydrosilyl(bis tetramethylcyclopentadienyl)Hafniumdimethyl,-   μ-Dimethylsilyl(tetramethylcyclopentadienyl)(3-propyltrimethylcyclopentadienyl)Hafniumdimethyl,    and-   μ-Dicyclopropylsilyl(bis    tetramethylcyclopentadienyl)Hafniumdimethyl.

In an alternate embodiment, the “dimethyl” after the transition metal inthe list of catalyst compounds above is replaced with a dihalide (suchas dichloride or difluoride) or a bisphenoxide, particularly for usewith an alumoxane activator.

Activators and Activation Methods for Catalyst Compounds

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract one reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxideor amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. Another alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst precursor (per metal catalytic site). Theminimum activator-to-catalyst-precursor is a 1:1 molar ratio. Alternatepreferred ranges include up to 500:1, alternately up to 200:1,alternately up to 100:1 alternately from 1:1 to 50:1.

Aluminum alkyl or organoaluminum compounds which may be utilized asco-activators (or scavengers) include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

Ionizing Activators

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, a tris perfluorophenyl boronmetalloid precursor or a tris perfluoronapthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459) or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators. Muchpreferred activators are the ionic ones, not the neutral boranes.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogens, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, napthyl ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is tris perfluorophenyl boron or trisperfluoronapthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

Ionic catalysts can be preparedly reacting a transition metal compoundwith some neutral Lewis acids, such as B(C₆F₆)₃, which upon reactionwith the hydrolyzable ligand (X) of the transition metal compound formsan anion, such as ([B(C₆F₅)₃(X)⁻]), which stabilizes the cationictransition metal species generated by the reaction. The catalysts canbe, and preferably are, prepared with activator components which areionic compounds or compositions.

Compounds useful as an activator component in the preparation of theionic catalyst systems used in the process of this invention comprise acation, which is preferably a Bronsted acid capable of donating aproton, and a compatible non-coordinating anion which anion isrelatively large (bulky), capable of stabilizing the active catalystspecies (the Group 4 cation) which is formed when the two compounds arecombined and said anion will be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated substrates or otherneutral Lewis bases such as ethers, amines and the like. Two classes ofcompatible non-coordinating anions have been disclosed in EP-A0 277,003and EP-A0 277,004 published 1988: 1) anionic coordination complexescomprising a plurality of lipophilic radicals covalently coordinated toand shielding a central charge-bearing metal or metalloid core, and 2)anions comprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L-H)_(d) ⁺(A^(d−))  (14)wherein L is an neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronstedacid; A^(d−) is a non-coordinating anion having the charge d−; and d isan integer from 1 to 3.

The cation component, (L-H)_(d) ⁺ may include Bronsted acids such asprotonated Lewis bases capable of protonating a moiety, such as an alkylor aryl, from the bulky ligand metallocene containing transition metalcatalyst precursor, resulting in a cationic transition metal species.

The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2 to 6; n−k=d; M is an element selected from Group 13 of thePeriodic Table of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronapthyl)borate, triethylamoniumtetrakis(perfluoronapthyl)borate, tripropylammoniumtetrakis(perfluoronapthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronapthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronapthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronapthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronapthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronapthyl)borate,tropillium tetrakis(perfluoronapthyl)borate, triphenylcarbeniumtetrakis(perfluoronapthyl)borate, triphenylphosphoniumtetrakis(perfluoronapthyl)borate, triethylsilyliumtetrakis(perfluoronapthyl)borate,benzene(diazonium)tetrakis(perfluoronapthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, anddialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and additional tri-substitutedphosphonium salts such as tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Most preferably, the ionic stoichiometric activator (L-H)_(d) ⁺ (A^(d−))is, N,N-dimethylanilinium tetrakis(perfluoronapthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronapthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetrakis(perfluorophenyl)borate.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing a bulky ligandmetallocene catalyst cation and their non-coordinating anion are alsocontemplated, and are described in EP-A 0 426 637, EP-A 0 573 403 andU.S. Pat. No. 5,387,568, which are all herein incorporated by reference.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to said cation or which is only weakly coordinated tosaid cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral fourcoordinate metallocene compound and a neutral by-product from the anion.Non-coordinating anions useful in accordance with this invention arethose that are compatible, stabilize the metallocene cation in the senseof balancing its ionic charge at +1, yet retain sufficient lability topermit displacement by an ethylenically or acetylenically unsaturatedmonomer during polymerization. In addition to these activator compoundsor co-catalysts, scavengers are used such as tri-isobutyl aluminum ortri-octyl aluminum.

Invention process also can employ cocatalyst compounds or activatorcompounds that are initially neutral Lewis acids but form a cationicmetal complex and a noncoordinating anion, or a zwitterionic complexupon reaction with the invention compounds. For example,tris(pentafluorophenyl)boron or aluminum act to abstract a hydrocarbylor hydride ligand to yield an invention cationic metal complex andstabilizing noncoordinating anion, see EP-A 0 427 697 and EP-A 0 520 732for illustrations of analogous Group-4 metallocene compounds. Also, seethe methods and compounds of EP-A 0 495 375. For formation ofzwitterionic complexes using analogous Group 4 compounds, see U.S. Pat.Nos. 5,624,878; 5,486,632; and 5,527,929.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(OX^(e+))_(d)(A^(d−))_(e)  (16)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis an integer from 1 to 3; and A⁻, and d are as previously defined.Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activators, especiallytetrakis(pentafluorophenyl)borate.

The typical NCA activator-to-catalyst-precursor ratio is a 1:1 molarratio. Alternate preferred ranges include from 0.1:1 to 100:1,alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1alternately from 1:1 to 1000:1. A particularly useful range is from0.5:1 to 10:1, preferably 1:1 to 5:1.

Activator Combinations

It is within the scope of this invention that catalyst compounds can becombined with one or more activators or activation methods describedabove. For example, a combination of activators have been described inU.S. Pat. Nos. 5,153,157 and 5,453,410, European publication EP-B1 0 573120, and PCT publications WO 94/07928 and WO 95/14044. These documentsall discuss the use of an alumoxane in combination with an ionizingactivator.

Oligomer Uses

The oligomers prepared herein may be functionalized by reacting ahereroatom containing group with the oligomer with or without acatalyst. Examples include catalytic hydrosilylation, hydroformylation,or hydroamination, or maleation with activators such as free radicalgenerators (e.g. peroxides). The functionalized oligomers can be used inoil additivation and many other applications. Preferred uses includeadditives for lubricants and or fuels. Preferred heteroatom containinggroups include, amines, aldehydes, alcohols, acids, succinic acid,maleic acid and maleic anhydride.

In some embodiments the oligomers produced herein are functionalized asdescribed in U.S. Pat. No. 6,022,929; A. Toyota, T. Tsutsui, and N.Kashiwa, Polymer Bulletin 48, 213-219, 2002; and J. Am. Chem. Soc.,1990, 112, 7433-7434.

In another embodiment this invention relates to:

-   1. A co-oligomer having an Mn of 300 to 30,000 g/mol comprising 10    to 90 mol % propylene and 10 to 90 mol % of ethylene, wherein the    oligomer has at least X % allyl chain ends (relative to total    unsaturations as measured by ¹H NMR), where: 1) X=(−0.94(mole %    ethylene incorporated)+100), when 10 to 60 mole % ethylene is    present in the co-oligomer, and 2) X=45, when greater than 60 and    less than 70 mole % ethylene is present in the co-oligomer, and 3)    X=(1.83*(mole % ethylene incorporated)−83), when 70 to 90 mole %    ethylene is present in the co-oligomer.-   2. The oligomer of paragraph 1 wherein the oligomer has more than    90% allyl chain ends (relative to total unsaturations).-   3. The oligomer of paragraph 1 wherein the oligomer comprises at 15    to 95 wt % ethylene and has more than 80% allyl chain ends (relative    to total unsaturations).-   4. The oligomer of paragraph 1 wherein the oligomer comprises at 30    to 95 wt % ethylene and has more than 70% allyl chain ends (relative    to total unsaturations).-   5. The oligomer of paragraph 1 wherein the oligomer comprises at 30    to 95 wt % ethylene and has more than 90% allyl chain ends (relative    to total unsaturations).-   6. A propylene oligomer, comprising more than 90 mol % propylene and    less than 10 mol % ethylene wherein the oligomer has: at least 93%    allyl chain ends, a number average molecular weight (Mn) of about    500 to about 20,000 g/mol, an isobutyl chain end to allylic vinyl    group ratio of 0.8:1 to 1.35:1.0, and less than 1400 ppm aluminum.-   7. A propylene oligomer, comprising: at least 50 mol % propylene and    from 10 to 50 mol % ethylene, wherein the oligomer has: at least 90%    allyl chain ends, an Mn of about 150 to about 10,000 g/mol, and an    isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0,    wherein monomers having four or more carbon atoms are present at    from 0 to 3 mol %.-   8. A propylene oligomer, comprising at least 50 mol % propylene,    from 0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % C₄ to C₁₂    olefin, wherein the oligomer has: at least 90% allyl chain ends, an    Mn of about 150 to about 10,000 g/mol, and an isobutyl chain end to    allylic vinyl group ratio of 0.8:1 to 1.35:1.0.-   9. A propylene oligomer, comprising at least 50 mol % propylene,    from 0.1 to 45 mol % ethylene, and from 0.1 to 5 mol % diene,    wherein the oligomer has: at least 90% allyl chain ends, an Mn of    about 150 to about 10,000 g/mol, and an isobutyl chain end to    allylic vinyl group ratio of 0.7:1 to 1.35:1.0.-   10. A homo-oligomer, comprising propylene, wherein the oligomer has:    at least 93% allyl chain ends, an Mn of about 500 to about 20,000    g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8:1    to 1.2:1.0, and less than 1400 ppm aluminum.-   11. The oligomer of any of paragraphs 1 to 10, wherein the oligomer    is a liquid at 25° C.-   12. The oligomer of any of paragraphs 1-11, wherein the Mn is about    500 to about 7,500 g/mol, the Mw is 1,000 to about 20,000 g/mol, and    the Mz is about 1400 (alternately 1700) to about 150,000 g/mol.-   13. The oligomer of any of paragraphs 1-12, wherein the oligomer has    no detectable melting point by DSC following storage at ambient    temperature for at least 48 hours.-   14. The oligomer of any of paragraphs 1-12, wherein the oligomer has    a melting peak of from about 60° C. to about 130° C.-   15. A homogenous process for making the propylene co-oligomer of any    of the above paragraphs 1 to 14, said process having productivity of    at least 4.5×10³ g/mmol/hr, wherein the process comprises:

contacting, at a temperature of from 35° C. to 150° C., propylene, 0.1to 70 mol % ethylene and from 0 to about 5 wt % hydrogen in the presenceof a catalyst system comprising an activator and at least onemetallocene compound represented by the formulae:

where

-   Hf is hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each Q is, independently carbon or a heteroatom, preferably C, N, P,    S (preferably at least one Q is a heteroatom, alternately at least    two Q's are the same or different heteroatoms, alternately at least    three Q's are the same or different heteroatoms, alternately at    least four Q's are the same or different heteroatoms);-   each R¹ is, independently, a C₁ to C₈ alkyl group, preferably a C₁    to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,    pentyl, hexyl, heptyl or octyl, R¹ may the same or different as R²;-   each R² is, independently, a C₁ to C₈ alkyl group, preferably a C₁    to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,    pentyl, hexyl, heptyl or octyl, preferably R¹ and/or R² are not    branched;-   each R³ is, independently, hydrogen, or a substituted or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    preferably 1 to 6 carbon atoms, preferably a substituted or    unsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however that    at least three R³ groups are not hydrogen (alternately four R³    groups are not hydrogen, alternately five R³ groups are not    hydrogen);-   each R⁴ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group, preferably a substituted or unsubstituted    hydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to    8 carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, substituted phenyl (such as propyl phenyl),    phenyl, silyl, substituted silyl, (such as CH₂SiR′, where R′ is a C₁    to C₁₂ hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl);-   R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided however that    at least seven R⁷ groups are not hydrogen, alternately at least    eight R⁷ groups are not hydrogen, alternately all R⁷ groups are not    hydrogen, (preferably the R⁷ groups at the 3 and 4 positions on each    Cp ring of Formula IV are not hydrogen);-   N is nitrogen;-   T is a bridge, preferably, Si or Ge, preferably Si;-   each R^(a), is independently, hydrogen, halogen or a C1 to C20    hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) can    form a cyclic structure including aromatic, partially saturated, or    saturated cyclic or fused ring system;-   and further provided that any two adjacent R groups may form a fused    ring or multicenter fused ring system where the rings may be    aromatic, partially saturated or saturated.-   16. A homogenous process for making the propylene homo-oligomer of    any of paragraphs 1- to 14, said process having a productivity of at    least 4.5×10⁶ g/mol/min, wherein the process comprises:

contacting, at a temperature of from 30° C. to 120° C., propylene, 0 mol% comonomer and from 0 to about 5 wt % hydrogen in the presence of acatalyst system comprising an activator and at least one metallocenecompound represented by the formulae:

where

-   Hf is hafnium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof, preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each Q is, independently carbon or a heteroatom, preferably C, N, P,    S (preferably at least one Q is a heteroatom, alternately at least    two Q's are the same or different heteroatoms, alternately at least    three Q's are the same or different heteroatoms, alternately at    least four Q's are the same or different heteroatoms);-   each R¹ is, independently, a C₁ to C₈ alkyl group, preferably a C₁    to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,    pentyl, hexyl, heptyl or octyl, R¹ may the same or different as R²;-   each R² is, independently, a C₁ to C₈ alkyl group, preferably a C₁    to C₈ linear alkyl group, preferably methyl ethyl, propyl, butyl,    pentyl, hexyl, heptyl or octyl, preferably R¹ and/or R² are not    branched;-   each R³ is, independently, hydrogen, or a substituted or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    preferably 1 to 6 carbon atoms, preferably a substituted or    unsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however    that: 1) all five R³ groups are methyl, or 2) four R³ groups are not    hydrogen and at least one R³ group is a C₂ to C₈ substituted or    unsubstituted hydrocarbyl (preferably at least two, three, four or    five R³ groups are a C₂ to C₈ substituted or unsubstituted    hydrocarbyl);-   each R⁴ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group, preferably a substituted or unsubstituted    hydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to    8 carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, substituted phenyl (such as propyl phenyl),    phenyl, silyl, substituted silyl, (such as CH₂SiR′, where R′ is a C₁    to C₁₂ hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl);-   R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided however that    at least seven R⁷ groups are not hydrogen, alternately at least    eight R⁷ groups are not hydrogen, alternately all R⁷ groups are not    hydrogen, (preferably the R⁷ groups at the 3 and 4 positions on each    Cp ring of Formula IV are not hydrogen);-   N is nitrogen;-   T is a bridge, preferably, Si or Ge, preferably Si;-   each R^(a), is independently, hydrogen, halogen or a C1 to C20    hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) can    form a cyclic structure including aromatic, partially saturated, or    saturated cyclic or fused ring system;-   and further provided that any two adjacent R groups may form a fused    ring or multicenter fused ring system where the rings may be    aromatic, partially saturated or saturated.-   17. The process of paragraph 15 or 16, wherein the activator    comprises one or more non-coordinating anions.-   18. The process of paragraph 15, 16, or 17 wherein the catalyst    system comprises one or more of (pentamethylcyclopentadienyl)(1,3    dimethylindenyl)hafnium)dimethyl, and    (pentamethylcyclopentadienyl)(1,3    dimethylindenyl)hafnium)dichloride.-   19. The process of paragraph 15 or 17, wherein the catalyst system    comprises one or more of    (1,3-Dimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3,4,7-Tetramethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3-Dimethylindenyl)(tetramethylcyclopentadienyl)Hafniumdimethyl,    (1,3-Diethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3-Dipropylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1-Methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3-Dimethylindenyl)(tetramethylpropylcyclopentadienyl)Hafniumdimethyl,    (1,2,3-Trimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3-Dimethylbenzindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (2,7-Bis    t-butylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (9-Methylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (2,7,9-Trimethylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    μ-Dihydrosilyl(bis tetramethylcyclopentadienyl)Hafniumdimethyl,    μ-Dihydrosilyl(bis tetramethylcyclopentadienyl)Hafniumdimethyl,    μ-Dimethylsilyl(tetramethylcyclopentadienyl)(3-propyltrimethylcyclopentadienyl)Hafniumdimethyl,    μ-Dicyclopropylsilyl(bis tetramethylcyclopentadienyl)Hafnium    dimethyl.    1,3-Dimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,3,4,7-Tetramethylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,3-Dimethylindenyl)(tetramethylcyclopentadienyl)Hafniumdihalide,    (1,3-Diethylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,3-Dipropylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1-Methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,3-Dimethylindenyl)(tetramethylpropylcyclopentadienyl)Hafniumdihalide,    (1,2,3-Trimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,3-Dimethylbenzindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (2,7-Bis    t-butylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (9-Methylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (2,7,9-Trimethylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    μ-Dihydrosilyl(bis tetramethylcyclopentadienyl)Hafniumdihalide,    μ-Dihydrosilyl(bis tetramethylcyclopentadienyl)Hafniumdihalide,    μ-Dihalidesilyl(tetramethylcyclopentadienyl)(3-propyltrimethylcyclopentadienyl)Hafniumdihalide,    and μ-Dicyclopropylsilyl(bis tetramethylcyclopentadienyl)Hafnium    dihalide.-   20. The process of paragraph 16 or 17, wherein the catalyst system    comprises one or more of    (1,3-Dimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3,4,7-Tetramethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3-Diethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3-Dipropylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1-Methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,2,3-Trimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3-Dimethylbenzindenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (2,7-Bis    t-butylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (9-Methylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (2,7,9-Trimethylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdimethyl,    (1,3-Dimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,3,4,7-Tetramethylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,3-Diethylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,3-Dipropylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1-Methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,2,3-Trimethylindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (1,3-Dimethylbenzindenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (2,7-Bis    t-butylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdihalide,    (9-Methylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdihalide, and    (2,7,9-Trimethylfluorenyl)(pentamethylcyclopentadienyl)Hafniumdihalide.-   21. The process of any of paragraphs 15 to 20, further comprising    functionalizing the propylene oligomer.-   22. The process of any of paragraphs 15 to 20, further comprising    functionalizing the propylene oligomer with succinic acid, maleic    acid, maleic anhydride or combinations thereof.

EXAMPLES

The foregoing discussion can be further described with reference to thefollowing non-limiting examples.

Product Characterization

Products were characterized by ¹H NMR and ¹³C NMR as follows:

¹³C NMR

¹³C NMR data was collected at 120° C. in a 10 mm probe using a Varianspectrometer with a ¹Hydrogen frequency of at least 400 MHz. A 90 degreepulse, an acquisition time adjusted to give a digital resolution between0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating was employed during the entire acquisitionperiod. The spectra were acquired using time averaging to provide asignal to noise level adequate to measure the signals of interest.Samples were dissolved in tetrachloroethane-d₂ at concentrations between10 to 15 wt % prior to being inserted into the spectrometer magnet.

Prior to data analysis spectra were referenced by setting the chemicalshift of the (—CH₂—)_(n) signal where n>6 to 29.9 ppm.

Chain ends for quantization were identified using the signals shown inthe table below. N-butyl and n-propyl were not reported due to their lowabundance (less than 5%) relative to the chain ends shown in the tablebelow.

Chain End ¹³CNMR Chemical Shift P~i-Bu 23-5 to 25.5 and 25.8 to 26.3 ppmE~i-Bu 39.5 to 40.2 ppm P~Vinyl 41.5 to 43 ppm E~Vinyl 33.9 to 34.4 ppm¹H NMR

¹H NMR data was collected at either room temperature or 120° C. (forpurposes of the claims, 120° C. shall be used) in a 5 mm probe using aVarian spectrometer with a ¹Hydrogen frequency of at least 400 MHz. Datawas recorded using a maximum pulse width of 45° C., 8 seconds betweenpulses and signal averaging 120 transients. Spectral signals wereintegrated and the number of unsaturation types per 1000 carbons wascalculated by multiplying the different groups by 1000 and dividing theresult by the total number of carbons. Mn was calculated by dividing thetotal number of unsaturated species into 14,000.

The chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Unsaturation Type Region (ppm) Number of hydrogens per structure Vinyl4.95-5.10 2 Vinylidene 4.70-4.84 2 Vinylene 5.31-5.55 2 Trisubstituted5.11-5.30 1

The populations of olefin unsaturations found in the products by ¹H NMRare summarized in Table 3. In this table, the vinyl population, as apercentage of total unsaturation, is provided as well, along with thenumber average molecular weight calculated by assuming one unsaturationper chain and degree of polymerization, or average number of propyleneunits per chain. For the propylene oligomer products, the % vinyl rangesfrom ˜0 (comparative examples A and B catalysts) to as high as ˜98% (F).Regardless of activator, the less sterically encumbered A, B catalysts(comparative examples) did not produce significant vinyl populations,and the metallocenes D, G and H also produce products with low allylicvinyl content (10 to 42%). In the case of E, the activator appears toimpact the chain termination pathway. In the case of F runs, highallylic vinyl populations were attained with both 1 and 4 activators,although allylic vinyl population decreased modestly with increasingpolymerization temperature. Temperature played a role in the % vinyl forE but less so for F. Where impact was observed, it was opposite to usingbridged, chiral metallocenes.

Glass Transition Temperature (Tg) was measured by DSC as describedabove.

Viscosity was measured at 35° C. using a Brookfield viscometer.

Refractive Index was measured at 25° C. with 589 nm Na line.

Materials

The following metallocenes were used:

-   A=bis(1-methyl,3-n-butylcyclopentadienyl)zirconium dimethyl;-   B=dimethylsilyl bis(4,5,6,7-tetrahydroindenyl)zircomium dimethyl;-   C=dimethylsilyl bis(indenyl)hafnium dimethyl;-   D=(tetramethylcyclopentadienyl)(1,3-dimethylindenyl)zirconium    dimethyl;-   E=(tetramethylcyclopentadienyl)(1,3-dimethylindenyl)hafnium    dimethyl;-   F=(pentamethylcyclopentadienyl)(1,3-dimethylindenyl)hafnium    dimethyl;-   G=(tetramethylcyclopentadienyl)(1-isopropylindenyl)hafnium dimethyl;-   H=(tetramethylcyclopentadienyl)(1-isopropyl,3-n-propylindenyl)hafnium    dimethyl; and-   J=dimethylsilyl bis(2-methyl,4-phenylindenyl)zirconium dimethyl.

Several ionic activators and one supported ionic activator were used toactivate the metallocenes. The ionic activators used were:

-   1=dimethylanilinium perfluorotetraphenylborate,-   2=4-tert-butylanilinium    bis(pentafluorophenyl)bis(perfluoro-2-napthyl)borate,-   3=4-tert-butylanilinium    (pentafluorophenyl)tris(perfluoro-2-napthyl)borate,-   4=dimethylanilinium tetrakis(perfluoro-2-napthyl)borate,-   5=dimethylanilinium tetrakis(3,5    (pentafluorophenyl)perfluorophenylborate); and-   6=tris-perfluorophenyl boron.

Catalyst Compound Synthesis: Typical dry-box procedures for synthesis ofair-sensitive compounds were followed. Solvents were purchased fromAldrich and dried over 2 A sieves. Indene was purchased from Aldrich andpentamethylcyclopentadiene was purchased from Norquay. Metallocenes A, Band C were purchased from Boulder scientific or Albemarle. Theactivators were purchased from Albemarle or Grace Davison.

Catalyst F: (CpMe₅)(1,3-Me₂C₉H₅)HfMe₂

LiC₉H₇ was generated in Et₂O (−35° C.) by the reaction of 29 g indene(0.25 mol) with 1 equivalent of n-BuLi (10 M, hexane) added slowly.LiC₉H₇ was isolated by reduction of the ether solution, addition ofhexane and filtration over a medium glass frit. The product was washedwith additional hexane (2×40 mL). LiC₉H₇ was dissolved in Et₂O, cooledto −35° C. and reacted with excess MeI (0.375 mol, 47.6 g). After 2hours the reaction mixture was warmed to ambient temperature. 1-MeC₉H₇was isolated as a colorless liquid by aqueous work-up and etherextractions. Similarly 1,3-Me₂C₉H₆ was synthesized by lithiation ofMeC₉H₇, methylation with MeI and aqueous work-up. [Li][1,3-Me₂C₉H₅] wassynthesized by reaction of 1,3-Me₂C₉H₆ in hexane with excess nBuLi (1.1equiv) for 12 hours. The white solid was filtered and washed withadditional hexane and dried in vacuo to yield pure [Li][1,3-Me₂C₉H₅], B(14.5 g). ¹H NMR (THF-d₈, 300 MHz) δ ppm; 7.25-7.10 (m, C₆H₄, 2H),6.45-6.30, C₆H₄, 2H), 6.10 (s, 2-indenyl proton, 1H), 2.35 (s,1,3Me₂C₉H₅, 6H).

CpMe₅HfCl₃ (Crowther, D.; Baenziger, N.; Jordan, R.; J. Journal of theAmerican Chemical Society (1991), 113(4), 1455-1457) (10.4 g) wasreacted with [Li][1,3-Me₂C₉H₅] (3.7 g, 24.8 mmol) in Et₂O (100 ml) for12 hours. The yellow product was collected by filtration over a glassfrit and dried to yield crude (CpMe₅)(1,3-Me₂C₉H₅)HfCl₂(8.6 g) as amixture with LiCl.

¹H NMR (CD₂Cl₂, 300 MHz) δ ppm; 7.58-7.11 (m, C₆H₄), 6.17 (s, 2-indenylproton), 2.32 (s, 1,3Me₂C₉H₅), 2.09 (s, CpMe₅).

Crude (CpMe₅)(1,3-Me₂C₉H₅)HfCl₂ (2.5 g) was slurried in toluene (100 ml)and reacted with MeMgI (4.2 g, 2.1 equiv, 3.0 M in Et₂O). The reactionmixture was heated to 80° C. for 3 hours. After cooling the volatileswere removed in vacuo to yield a solid which was extracted with hexane(4×40 mL). Hexane was removed from the combined extractions to yieldsolid yellow (CpMe₅)(1,3-Me₂C₉H₅)HfMe₂, E (1.6 g). ¹H NMR (C₆D₆, 300MHz) δ ppm; 7.55-7.48 (m, C₆H₄, 2H), 7.20-7.16 (m, C₉H₅, 3H), 2.00 (s,1,3Me₂C₉H₅, 6H), 1.76 (s, CpMe₅, 15H), −0.95 (s, Hf-Me, 6H).

Catalyst D: (CpMe₄)(1,3-Me₂C₉H₅)ZrMe₂

ZrCl₄ (36 g) was slurried in CH₂Cl₂ (200 mL) and then reacted with Me₂S(19.2 g) for 1 hour. CpMe₄HSiMe₃ (34 g) was added slowly to the reactionmixture. Yellow solid began to precipitate after several hours and wasfiltered to yield a first crop of 21.3 g of light yellow solid product.(CpMe₄H)ZrCl₃(SMe₂)_(x) ¹H NMR (CD₂Cl₂, 300 MHz) δ ppm; 6.05 (s,CpMe₄H), 2.6 (br s, MeS), 2.27 (s, CpMe₄), 2.20 (s, CpMe₄).

(CpMe₄H)ZrCl₃ (15.0 g) was slurried in Et₂O (250 mL) and reacted with[Li][1,3-Me₂C₉H₅] (7.5 g) for 16 hours. The reaction product wasfiltered over a glass frit, washed with CH₂Cl₂ and dried in vacuo. Allthe solid product (ca 22 g) was slurried in Et₂O (200 mL) and reactedwith MeMgI (38 g 3 M in Et₂O). After 4 hours dimethoxyethane (6.8 g) wasadded and the reaction mixture filtered. Additional Et₂O was used toextract the solid residue. The filtrates were reduced and cooled to −35°C. An off-white solid product was filtered and dried in vacuo (14.8 g).(CpMe₄)(1,3-Me₂C₉H₅)ZrMe₂.

¹H NMR (CD₂Cl₂, 500 MHz) δ ppm; 7.35, 7.05 (m, C₉H₅), 5.51 (s, C₉H₅),4.83 (s, CpMe₄H), 2.17 (s, Me₂C₉H₅), 1.79, 1.70 (s, CpMe₄H), −1.31 ZrMe.

Catalyst E: (CpMe₄)(1,3-Me₂C₉H₅)HfMe₂

HfCl₄ (31 g) was slurried in CH₂Cl₂ (200 mL) and reacted slowly withCpMe₄HSiMe₃ for several hours. The reaction mixture was filtered,reduced in volume and hexane (80 mL) was added. The filtrate was cooledto −35° C. The off-white product was collected and dried in vacuo.(CpMe₄H)HfCl₃ (8.0 g) was dissolved in Et₂O (150 mL) and reacted with[Li][1,3-Me₂C₉H₅] (2.8 g). After 1 hour the volatiles were removed andthe crude reaction mixture extracted with CH₂Cl₂ (2×60 mL). The filtratewas reduced in vacuo to a light yellow solid product (7.2 g). All(CpMe₄)(1,3-Me₂C₉H₅)HfCl₂ (7.2 g) was slurried in toluene (200 mL) andreacted with 2 equivalents of MeMgBr (3 M in Et₂O). The reaction mixturewas heated to 90° C. for 6 hours. The mixture was cooled to roomtemperature and dimethoxyethane (3 ml) was added. The volatiles wereremoved, the residue extracted with CH₂Cl₂ and the filtrates werereduced in vacuo. The product was collected after cooling to −35° C.(2.85 g). (CpMe₄)(1,3-Me₂C₉H₅)HfMe₂ ¹H NMR (CD₂Cl₂, 500 MHz) δ ppm;7.35, 7.06 (m, C₉H₅), 5.50 (s, C₉H₅), 4.89 (s, CpMe₄H), 2.18 (s,Me₂C₉H₅), 1.79, 1.76 (s, CpMe₄H), −1.49 HfMe.

Catalyst H: (tetramethylcyclopentadienyl)(1-isopropyl,3-propyl-C₉H₆)HfMe₂

1-isopropyl, 3-propyl-C₉H₆ was synthesized by reaction of1-isopropylindenyl lithium with propyl bromide in Et₂O. The lithium saltis synthesized from BuLi in Et₂O. [Li][1-isopropyl, 3-propyl-C₉H₅] (2.1g) was dissolved in Et₂O (60 mL) and reacted with (CpMe₄H)HfCl₃ (4.0 g).MeMgI (2 equivalents) were added to the reaction mixture, 60 ml tolueneadded and the reaction was heated to 90° C. After 2 hours the reactionwas cooled, volatiles removed and the dimethyl product extracted withhexane. The product was obtained as an amber oil (3.8 g). ¹H NMR (C₆D₆,300 MHz) δ ppm; 7.48 (d), another doublet partially obscured undersolvent 7.02 (m), 5.53 (s), 4.72 (s), 3.25 (p), 2.72 (m), 2.31 (m),2.83, 2.77, 2.74, 2.73 (s), 1.22 (d), 1.07 (d), −0.73 (s, Hf-Me), −1.29(s, Hf-Me).

Catalyst G: (CpMe₄)(1-iC₃H₇—C₉H₅)HfMe₂

1-Isopropylindenyl lithium (Bradley et al, OM, 2004, 23, 5332) (2.0 g)was slurried in Et₂O (100 mL) and reacted with (CpMe₄H)HfCl₃ (5.0 g) for12 hours. The solid product was filtered and washed with hexane (3.7 g).(CpMe₄)(1-iC₃H₇—C₉H₅)HfCl₂ ¹H NMR (C₆D₆, 300 MHz) δ ppm; 7.55, 7.41 (d),6.95 (p), 6.22 (d), 5.51 (d), 4.96 (s), 3.72 (p), 1.93, 1.92, 1.83, 1.64(s), 1.34, 1.11 (d).

The dichloride was slurried in toluene (50 mL) and reacted with 2equivalents of MeMgI (3 M in Et₂O). The reaction was heated to 90° C.for 2 hours and then cooled. The volatiles were removed. The crudemixture was extracted with hexane (2×40 mL), filtered and filtratereduced to solid product in vacuo (3.1 g). ¹H NMR (C₆D₆, 300 MHz) δ ppm;−0.52, −1.46 Hf-Me.

TEAL-SiO₂:

SiO₂ Davison 948 calcined at 600° C. was slurried in hexane (30 mL) andreacted with Triethylaluminum (10 mL, 1.9 M in toluene) for 12 hours.The solid was filtered and washed with hexane (2×20 mL). After drying invacuo the yield was 10.75 g TEAL-SiO₂.

Catalyst I

TEAL-SiO₂ (2.0 g) was slurried in toluene (30 mL) and reacted withTriphenylcarbonium tetrakisperfluorophenyl borate (142 mg, GraceDavison) for 10 minutes. Metallocene E (56 mg) was added as a solutionin toluene (5 mL) to the slurry and allowed to react for 12 hours. Thesupported catalyst was filtered, washed with hexane and dried in vacuo.

Catalyst K

Similar to Catalyst I, Metallocene E was supported as described aboveexcept that 3.8 g TEAL-SiO₂, 215 mg of ionic activator 1, and 114 mg ofmetallocene E were used.

Polymerizations

Propylene oligomer batch or continuous polymerizations were carried outfor this study using a 2 L stirred autoclave reactor are described inTable 1. Catalyst solutions were prepared in a dry nitrogen purgedVacuum Atmospheres dry box by adding nearly equimolar (typically1.00:1.05) quantities of metallocene and activator to 4 mL dry toluenein a 10 mL glass vial. The mixture was stirred for several minutes andthen transferred to a clean, oven dried catalyst tube. An example of thebasic polymerization procedure follows: 2 mL of 25 wt %tri-n-octyl-aluminum (0.037 g Al) in hexanes as scavenger and 100 mLpropylene were added to the reactor. Next the reactor was heated to theselected polymerization temperature and catalyst/activator was flushedfrom the catalyst tube into the reactor with 100 mL propylene.Additional propylene was optionally added for a total of up to 1000 mL.In some cases, hydrogen was also added from a ballast tank (see Table2A). Hydrogen partial pressure was as high as 50 psig at the start ofthe run. Polymerization was carried out for 10 to 60 minutes, and thenthe reactor was cooled, depressurized, and opened. At this point thecollected product typically contained some residual monomer. Theresidual monomer concentration in the product was initially reduced by“weathering.” In many cases the sample was heated in the oven undernitrogen purge or for a short time with applied vacuum. Some of thelowest molecular weight oligomer product may be lost along with theresidual monomer. In some cases, residual monomer is still detected inthe product in ¹H NMR spectras recorded at 30° C. (but is not detectedwhen spectra are recorded at 120° C.). In the Tables below Polig meanspropylene oligomer, EP means propylene-ethylene oligomer, T_(p) meanspolymerization temperature, P-time means polymerization time, Cat meanscatalyst, Act means activator, DP means degree of polymerization.

TABLE 1 Summary of Propylene Polymerizations Tp P-time Yield AdditionalExample Product Cat Act Cat/Act (mg/mg) (° C.) (min) (g) C3**  1# PoligA 4 30/60   90 10 25 ***  2# Polig B 4 10/25   90 7 110 ***  3# Polig A4 30/60   140 10 25 ***  4# Polig C 4 10/25   140 8 160 ***  5# Polig B4 4/12  145 7 140 ***  6# Polig B 1 6/15  152 5 47 ***  7# Polig B 16/15  130 10 30 ***  8 Polig D 4  6/13.1 132 10 5.7 ***  9 Polig E 410/25.7 132 10 19 *** 10 Polig E 4 10/25.7 100 12 31.9 100 11 Polig E 410/25.7 80 12 52.5 100 12 Polig E 4 10/25.7 80 27 142 400 13 Polig E 410/25.7 60 10 65 *** 14 Polig E 4 12/30.8 75 40 242 500 21 Polig E 110/17.9 132 10 17.9 *** 22 Polig E 1 10/17.9 80 12 46.2 100 23 Polig E 410/25.7 80 27 ~127 300 24 Polig D 4 10/31.5 80 10 8.9 150 26 Polig E 610/11.5 80 30 0 *** 25{circumflex over ( )} Polig K (150 mg) 80 30 9.8250 28{circumflex over ( )} Polig  I (210 mg) 60 30 14.9 *** 27 Polig E6 10/11.5 132 30 0 *** 30 Polig E 5 10/45.7 80 30 162 450 31 Polig E 210/23.1 80 30 112 350 32 Polig E 3 10/25.7 80 30 112 250 36 Polig E 110/17.9 45 30 130 *** 37 Polig H 4 10/25   80 30 13.2 200 38 Polig F 410/25   80 30 46.2 250 39 Polig G 4 10/22.7 80 25 70 150 40 Polig G 410/22.7 100 30 55.7  70 41 Polig G 4 10/22.7 132 30 16.2  40 42 Polig E4 10/25.7 38 20 ~200 *** 44 Polig E 4 10/25   60 30 ~75 *** 45 Polig E 410/25   37 30 ~85 *** 46 Polig E 4 10/25   100 30 36.7  80 47 Polig E 410/25   132 30 ~10 *** 48 Polig E 1 10/18   60 30 ~110 *** 49 Polig E 110/18   80 30 ~70 280 50 Polig E 4 10/25   60 180 ~200 *** 51 Polig E 110/18   60 120 ~220 *** #comparative, {circumflex over ( )}supported,**Additional propylene added, *** Continuous run using continuouspropylene feed from day tank

Propylene-Ethylene Co-Oligomerizations,

carried out for this study using a 2 L stirred autoclave reactor, aredescribed in Table 2. Catalyst solutions were prepared in a dry nitrogenpurged Vacuum Atmospheres dry box by adding nearly equimolar (typically1.00:1.05) quantities of metallocene and activator to 4 mL dry toluenein a 10 mL glass vial. The mixture was stirred for several minutes andthen transferred to a clean, oven dried catalyst tube. An example of thebasic polymerization procedure follows: 2 mL of 25 wt %tri-n-octyl-aluminum in hexanes as scavenger and 300 mL propylene wereadded to the reactor. Next the reactor was heated to appropriatepolymerization temperature and catalyst/activator was flushed from thecatalyst tube into the reactor with an additional 300 mL propylene.Ethylene was then added continuously throughout the reaction at partialpressures from less than 5 psi up to 220 psi. After a pre-determinedreaction time, the reactor was cooled, depressurized, and opened. Atthis point the collected product typically contained some residualmonomer. The residual monomer concentration in the product was initiallyreduced by “weathering.” In many cases the sample was heated in the ovenunder nitrogen purge or for a short time with applied vacuum. Some ofthe lowest molecular weight oligomer product may be lost along with theresidual monomer. Note that catalyst productivities are 28 to 678 timeshigher than the productivities reported by in Macromolecules 2008 41,559-567.

TABLE 2 Summary of Propylene-Ethylene Copolymerizations Catalyst/ MoleT_(p), Psig Time, Productivity, Example Activator metallocene^(a) ° C.C₂ ⁼ min Yield, g g/mmol/hr 33 E/4 2.13E−05 65 20 10 320 90,122 35 E/44.26E−06 60 40 20 127 89,526 52 F/4 8.26E−06 60 40 20 240 87,297 53 F/48.26E−06 65 30 10 128 92,838 54 F/4 4.13E−06 60 20 10 178 258,206 55 F/12.06E−06 58 <5 30 95 92,055 56 F/1 2.06E−06 70 <5 30 87 84,303 57 F/16.19E−06 70 10 60 80 12,920 58 F/1 8.26E−06 68 30 10 158 114,597 59 F/14.13E−06 65 50 10 95 137,806 60 F/1 2.07E−06 55 220 10 108 313,329 61F/1 4.15E−06 65 50 5 46 133,455 ^(a)in all cases, slight molar excess(~5-10 mole %) of activator used with metallocene.

TABLE 2A Propylene Polymerizations with Catalyst F in the Presence ofHydrogen Cat/Activator H₂, Tp. Time Yield Productivity Ex Act (mg/mg)psi (C.) (min) (g) g/mmol/hr 62 4 10/25 7 80 10 342 39768 63 4   5/12.57 27 60 348 13489 64 4  4/10 7 60 30 225 21803 65 4  4.5/11.25 7 40 45428 24579 66 1 5/9 7 29 50 525 33915 67 1   2/3.5 7 60 60 165 22841 68 1  6/10.4 7 45 30 487 45375 69 1   2/3.5 7 40 10 1.5 2180 70 1   2/3.5 5040 5 2.3 6689 71 1 4/7 7 50 10 140 101740 72 1 4/7 22 45 10 202 14677073 1 4/7 50 42 5 30 43622 74 1 4/7 50 47 30 325 78731

TABLE 3 Characterization Data for Propylene Oligomers % Tg Viscosity atRefractive Example Vinyls* DP* Mn* (° C.) 35° C. (cps) Index 1 3.3512.55 526.91 2 5.5 107.5 4516 3 1.50 6.57 275.92 4 28.7 86.1 3618 5 12.624.2 1017 6 1.94 6.54 274.51 7 1.64 6.93 291.18 8 14.19 8.23 345.51 925.03 4.34 182.43 1.4240 10 41.47 6.89 289.26 3.5 11 57.17 8.95 375.9412 55.74 9.01 378.28 16.0 13 73.30 26.97 1132.69 −37.3 14 69.63 14.40604.75 21 30.75 3.54 148.48 22 54.24 7.80 327.72 37.3 1.4489 23 60.888.46 355.15 1.4534 24 24.72 46.04 1933.70 −56.9 25 54.11 9.05 379.92 2863.3 17.48 734.1 29 16.1 45.8 1923 30 55.52 8.52 357.69 31 57.49 8.54358.70 32 60.45 9.33 391.83 36 62.37 68.17 2862.99 −16.7 37 10.68 8.07338.90 38 97.20 4.62 194.04 1.4252 39 42.16 7.61 319.42 40 27.06 4.68196.63 1.4298 41 15.14 3.59 150.81 42 74.12 106.5 4472.84 44 97.48 7.12299.02 45 97.61 24.12 1013.02 46 95.02 4.31 181.21 1.4367 47 88.73 3.79159.25 48 97.49 8.52 357.87 49 97.85 4.68 196.41 1.4205 50 96.24 8.14341.96 51 97.13 8.24 346.28 1.4422 62 97.1 6.31 265 63 96.5 22.49 945 6496.7 6.55 275 65 98.2 13.59 570 66 97.2 19.97 838 67 98.0 6.21 261 6897.4 10.31 433 71 98.0 6.79 285.4 72 98.2 7.52 315.7 73 96.7 10.56 443.574 97.4 9.07 380.8 % Vinyls = % allyl chain ends, *¹H NMR, IBCE =isobutyl chain end.

TABLE 3A GPC-DRI (PP standard) ¹H NMR GPC-DRI (PP Std) Ex. H₂, psi M_(N)M_(N) M_(W) M_(Z) 2 0 4516 3245 9600 21306 4 0 3617 3262 9584 22496 5 01017 576 2745 12604 13 0 1133 811 7546 675,306 24 0 1934 360 12,359614,945 33 0 1283 947 3,703 10,279 35 0 4546 4,080 19,065 313,648 36 02863 2,075 13,793 1,541,001 42 0 4473 3,410 26,362 180,129 45 0 1013.02504 2,409 9,196 63 0 945 468 1,736 4,143 64 7 275 106 265 611 65 7 570255 850 1,883 66 7 838 389 1,810 4,557 67 7 261 98 198 431 68 7 433 183538 1,142 71 7 285.4 134 395 1,676 72 50 315.7 153 443 1,600 73 7 443.5102 288 1,143 74 22 380.8 156 564 1,440 52 0 773 378 2,277 22,624 53 0929 466 9,804 53,617 54 0 795 315 3,577 38,176 55 0 974 651 3,290 23,90656 0 490 294 1,292 9,395 57 0 112 490 5,208 31,162 58 0 1071 501 6,70965,024 59 0 1580 633 11,053 118,559 60 0 4861 3,519 71,123 433,478 61 01877 900 16,764 348,185

TABLE 4 Properties of Propylene-Ethylene Copolymers Mole fraction Wtfraction propylene in propylene in Tg Sample product* product* (° C.) %vinyls* DP* Mn* 33 — — −45.6 82.5 30.6 1283 35 0.555 0.652 −53.1 84.1108.2 4545 52 0.629 0.718 −88 95.9 18.4 773 53 0.447 0.578 97.2 22.1 92954 0.501 0.606 96.4 18.9 795 55 0.428 0.529 −83 95.9 23.2 974 56 0.6110.702 94.6 11.7 490 57 0.434 0.535 94.9 26.8 1124 58 0.378 0.472 94.825.5 1071 59 0.351 0.447 96.5 37.6 1580 60 0.124 0.176 76.4 115.7 486161 0.247 0.329 99.1 44.7 1877 *Calculated from ¹H NMR % Vinyls = % allylchain ends

Examples 35 and 52-61 were characterized by ¹³C NMR as described abovethen compared to the data in Macromolecules 2008 41, 559-567.

TABLE 5 Allyl chain ends in Propylene-Ethylene Co-oligomers Source Wt %ethylene Mol % ethylene % allyl chain ends M-Tab 1† 0.0 0.00 100 M-Tab1† 21.4 29.0 65.0 M-Tab 1† 29.9 39.0 60.0 M-Tab 1† 51.0 61.0 43.0 CoatesTab 1† 54.2 64.0 42.0 35 34.8 44.5 84.1 52 28.2 37.1 95.9 53 42.2 55.397.2 54 39.4 49.9 96.4 55 47.1 57.2 95.9 56 29.8 38.9 94.6 57 46.5 56.694.9 58 52.8 62.2 94.8 59 55.3 64.9 96.5 60* 82.4 87.6 76.4* 61 67.175.3 99.1 M-Tab is table 1 of † Macromolecules 2008 41, 559-567 *10Cexotherm

TABLE 6 percent Chain End Microstructures from ¹³C NMR SaturatedUnsaturated End Groups* End Groups Sample IB-P IB-E Vinyl-P Vinyl-EInit/Term 52 71.8 28.2 71.7 28.3 1.31 53 64.5 35.5 64.1 35.9 1.32 5548.6 51.4 61.8 38.2 1.16 56 62.4 37.6 65.6 34.4 1.03

Saturated chain end microstructure analysis reveals the surprisingresult that propylene is nearly always the first monomer insertedfollowing β-Methyl elimination or transfer involving a growing chainand/or incoming monomer, even in polymers containing up to 52 mole %ethylene.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.

What is claimed is:
 1. A co-oligomer having an Mn of 300 to 30,000 g/mol(measured by ¹H NMR) comprising 10 to 50 mol % propylene and 50 to 90mol % of ethylene, wherein the co-oligomer has at least X % allyl chainends (relative to total unsaturations), where: 1) X=1.20*(−0.94*(mole %ethylene incorporated)+100), when 50 to 60 mole % ethylene is present inthe co-oligomer, and 2) X=45, when greater than 60 and less than 70 mole% ethylene is present in the co-oligomer, and 3) X=(1.83*(mole %ethylene incorporated)−83), when 70 to 90 mole % ethylene is present inthe co-oligomer; wherein the co-oligomer has been functionalized byreacting a heteroatom containing group with the co-oligomer, with orwithout catalyst.
 2. The co-oligomer of claim 1, wherein the co-oligomerhas more than 90% allyl chain ends (relative to total unsaturations). 3.The co-oligomer of claim 1, wherein the co-oligomer has more than 80%allyl chain ends (relative to total unsaturations).
 4. The co-oligomerof claim 1, wherein the co-oligomer has more than 70% allyl chain ends(relative to total unsaturations).
 5. The co-oligomer of claim 1,wherein the co-oligomer has more than 95% allyl chain ends (relative tototal unsaturations).
 6. The co-oligomer of claim 1, wherein theco-oligomer has at least 80% isobutyl chain ends.
 7. The co-oligomer ofclaim 1, wherein the co-oligomer has an Mw/Mn by GPC-DRI of 1.5 to 20and an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.35:1.0.
 8. The co-oligomer of claim 1, wherein the co-oligomer has anisobutyl chain end to allylic chain end ratio of 0.8:1 to 1.35:1.0. 9.The co-oligomer of claim 1, wherein the co-oligomer has an isobutylchain end to allylic chain end ratio of 0.9:1 to 1.2:1.0.
 10. Theco-oligomer of claim 1, wherein the co-oligomer has an isobutyl chainend to allylic chain end ratio of 0.9:1 to 1.1:1.0.
 11. The co-oligomerof claim 1, wherein the co-oligomer is a liquid at 25° C.
 12. Theco-oligomer of claim 1, wherein the Mn is about 500 to about 7,500g/mol, the Mw is 1,000 to about 20,000 g/mol, and the Mz is about 1400to about 150,000 g/mol.
 13. The co-oligomer of claim 1, wherein theMw/Mn is 1.7 to
 20. 14. The co-oligomer of claim 1, wherein the Mw/Mn is1.7 to
 10. 15. The co-oligomer of claim 1, wherein the co-oligomer has anumber average molecular weight (Mn) of about 600 to about 15,000 g/mol.16. The co-oligomer of claim 1, wherein the co-oligomer has an Mn ofabout 400 to about 10,000 g/mol.
 17. The co-oligomer of claim 1, whereinX is 95%.
 18. The co-oligomer of claim 1, wherein the co-oligomer has aTg of 0° C. or less.
 19. The co-oligomer of claim 1, wherein theco-oligomer has a melting point of from 60 to 130° C.
 20. A co-oligomerhaving an Mn of 300 to 30,000 g/mol (measured by ¹H NMR) comprising 15to 50 mol % propylene and 50 to 85 mol % of ethylene, wherein theco-oligomer has at least X % allyl chain ends (relative to totalunsaturations), where: 1) X=(−0.94*(mole % ethylene incorporated)+100)),when 50 to 60 mole % ethylene is present in the co-oligomer, and 2)X=50, when greater than 60 and less than 70 mole % ethylene is presentin the co-oligomer, and 3) X=(1.20(1.83*(mole % ethyleneincorporated)−83)), when 70 to 90 mole % ethylene is present in theco-oligomer; wherein the co-oligomer has been functionalized by reactinga heteroatom containing group with the co-oligomer, with or withoutcatalyst.
 21. The co-oligomer of claim 20 where the co-oligomer has a Tgof 0° C. or less.
 22. A co-oligomer having an Mn of 300 to 30,000 g/mol(measured by ¹H NMR) comprising 10 to 50 mol % propylene and 50 to 90mol % of ethylene, wherein the co-oligomer has at least X % allyl chainends (relative to total unsaturations), where: 1) X=(1.50(−0.94*(mole %ethylene incorporated)+100)), when 50 to 60 mole % ethylene is presentin the co-oligomer, and 2) X=60, when greater than 60 and less than 70mole % ethylene is present in the co-oligomer, and 3) X=(1.50(1.83*(mole% ethylene incorporated)−83)), when 70 to 90 mole % ethylene is presentin the co-oligomer; wherein the co-oligomer has been functionalized byreacting a heteroatom containing group with the co-oligomer, with orwithout catalyst.
 23. The co-oligomer of claim 22, wherein theheteroatom containing group is an amine, an aldehyde, an alcohol, or anacid.
 24. The co-oligomer of claim 22, wherein the heteroatom containinggroup is succinic acid, maleic acid or maleic anhydride.
 25. A lubricantor fuel comprising the co-oligomer of claim
 22. 26. A lubricant or fuelcomprising the co-oligomer of claim
 23. 27. A lubricant or fuelcomprising the co-oligomer of claim
 24. 28. The co-oligomer of claim 22where the co-oligomer has a Tg of 0° C. or less.
 29. A homogenousprocess for making a propylene co-oligomer, said process havingproductivity of at least 4500 g/mmol/hr, wherein the processcomprises: 1) contacting, at a temperature of from 35° C. to 150° C.,propylene, 0.1 to 70 mol % ethylene and from 0 to about 5 wt % hydrogenin the presence of a catalyst system comprising an activator and atleast one metallocene compound represented by at least one of theformulae:

where: Hf is hafnium; each X is, independently, selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes,amines, phosphines, ethers, and a combination thereof, and two X's mayform a part of a fused ring or a ring system; each Q is, independentlycarbon or a heteroatom; each R¹ is, independently, a C₁ to C₈ alkylgroup, R¹ may the same or different as R²; each R² is, independently, aC₁ to C₈ alkyl group; each R³ is, independently, hydrogen, or asubstituted or unsubstituted hydrocarbyl group having from 1 to 8 carbonatoms, provided that at least three R³ groups are not hydrogen; each R⁴is, independently, hydrogen or a substituted or unsubstitutedhydrocarbyl group, a heteroatom or heteroatom containing group; R⁵ ishydrogen or a C₁ to C₈ alkyl group; R⁶ is hydrogen or a C₁ to C₈ alkylgroup; each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,provided that at least seven R⁷ groups are not hydrogen; T is a bridge;each R^(a), is independently, hydrogen, halogen or a C₁ to C₂₀hydrocarbyl, and two R^(a) can form a cyclic structure includingaromatic, partially saturated, or saturated cyclic or fused ring system;and further provided that any two adjacent R groups may form a fusedring or multicenter fused ring system where the rings may be aromatic,partially saturated or saturated; and 2) obtaining a co-oligomer havingan Mn of 300 to 30,000 g/mol (measured by ¹H NMR) comprising 10 to 50mol % propylene and 50 to 90 mol % of ethylene, wherein the co-oligomerhas at least X % allyl chain ends (relative to total unsaturations),where: 1) X=1.20*(−0.94*(mole % ethylene incorporated)+100), when 50 to60 mole % ethylene is present in the co-oligomer, and 2) X=45, whengreater than 60 and less than 70 mole % ethylene is present in theco-oligomer, and 3) X=(1.83*(mole % ethylene incorporated)−83), when 70to 90 mole % ethylene is present in the co-oligomer.
 30. The process ofclaim 29, wherein the activator comprises one or more non-coordinatinganions.
 31. The process of claim 29, wherein the catalyst systemcomprises one or more of (pentamethylcyclopentadienyl)(1,3dimethylindenyl)hafnium dimethyl, and (pentamethylcyclopentadienyl)(1,3dimethylindenyl)hafnium)dichloride.
 32. The process of claim 29, whereinthe catalyst system comprises one or more of(1,3-dimethylindenyl)(pentamethylcyclopentadienyl)hafnium dimethyl,(1,3,4,7-tetramethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl, (1,3-dimethylindenyl)(tetramethylcyclopentadienyl)hafniumdimethyl, (1,3-diethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl, (1,3-dipropylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(1-methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,(1,3-dimethylindenyl)(tetramethylpropylcyclopentadienyl)hafniumdimethyl, (1,2,3-trimethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl, (1,3-dimethylbenzindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl, (9-methylfluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl, μ-dihydrosilyl(bis-tetramethylcyclopentadienyl)hafniumdimethyl,μ-dimethylsilyl(tetramethylcyclopentadienyl)(3-propyltrimethylcyclopentadienyl)hafniumdimethyl, μ-dicyclopropylsilyl(bis-tetramethylcyclopentadienyl)hafniumdimethyl, (1,3-dimethylindenyl)(pentamethylcyclopentadienyl)hafniumdihalide,(1,3,4,7-tetramethylindenyl)(pentamethylcyclopentadienyl)hafniumdihalide, (1,3-dimethylindenyl)(tetramethylcyclopentadienyl)hafniumdihalide, (1,3-diethylindenyl)(pentamethylcyclopentadienyl)hafniumdihalide, (1,3-dipropylindenyl)(pentamethylcyclopentadienyl)hafniumdihalide,(1-methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)hafniumdihalide,(1,3-dimethylindenyl)(tetramethylpropylcyclopentadienyl)hafniumdihalide, (1,2,3-trimethylindenyl)(pentamethylcyclopentadienyl)hafniumdihalide, (1,3-dimethylbenzindenyl)(pentamethylcyclopentadienyl)hafniumdihalide, (9-methylfluorenyl)(pentamethylcyclopentadienyl)hafniumdihalide, μ-dihydrosilyl(bis-tetramethylcyclopentadienyl)hafniumdihalide, μ-dihydrosilyl(bis-tetramethylcyclopentadienyl)hafniumdihalide,μ-dimethylsilyl(tetramethylcyclopentadienyl)(3-propyltrimethylcyclopentadienyl)hafniumdihalide, andμ-dicyclopropylsilyl(bis-tetramethylcyclopentadienyl)hafnium dihalide.33. The process of claim 29, further comprising functionalizing thepropylene co-oligomer.
 34. The process of claim 29, further comprisingfunctionalizing the propylene co-oligomer with succinic acid, maleicacid, maleic anhydride or combinations thereof.
 35. The process of claim29, wherein the propylene co-oligomer has a Tg of 0° C. or less.
 36. Theprocess of claim 29, wherein the propylene co-oligomer has a meltingpoint of from 60 to 130° C.